CN110415863B - Hard coat film, transparent conductive film laminate, and image display device - Google Patents

Hard coat film, transparent conductive film laminate, and image display device Download PDF

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Publication number
CN110415863B
CN110415863B CN201910284583.8A CN201910284583A CN110415863B CN 110415863 B CN110415863 B CN 110415863B CN 201910284583 A CN201910284583 A CN 201910284583A CN 110415863 B CN110415863 B CN 110415863B
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hard coat
transparent conductive
film
layer
mass
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CN110415863A (en
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松本圭祐
竹下翔也
安藤豪彦
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Nitto Denko Corp
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Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

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  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

The present invention relates to a hard coat film, a transparent conductive film laminate, and an image display device. The hard coat film comprises a transparent base material and a hard coat layer arranged on one side of the transparent base material in the thickness direction. The hard coat layer contains silica particles, zirconia particles, and a resin, wherein the content ratio of the silica particles in the hard coat layer is 0.5 mass% or more and less than 3.0 mass%, and the content ratio of the zirconia particles in the hard coat layer is 35.0 mass% or more and less than 70.0 mass%.

Description

Hard coat film, transparent conductive film laminate, and image display device
Technical Field
The present invention relates to a hard coat film, a transparent conductive film laminate, and an image display device.
Background
Heretofore, a transparent conductive film in which a transparent conductive layer such as an indium tin composite oxide is formed on a transparent substrate so as to form a desired electrode pattern has been used for optical applications such as a touch panel.
For example, japanese patent application laid-open No. 2017-62609 discloses a transparent conductive film including a transparent resin film, a hard coat layer, an optical adjustment layer, and a transparent conductive layer in this order. In such a transparent conductive film, a hard coat layer is provided to impart scratch resistance to the transparent conductive film, and an optical adjustment layer is provided to prevent the electrode pattern from being recognized. In addition, in the transparent conductive film, a transparent conductive layer is laminated on a transparent base material having good mechanical strength such as PET.
Disclosure of Invention
In recent years, however, from the viewpoint of reducing (halving) the difference between the amount of light passing through the electrode pattern (pattern portion) and the amount of light passing through the portion other than the electrode pattern (non-pattern portion) and making it easier to suppress the visibility of the electrode pattern, image display devices have been studied in which a transparent conductive film is disposed on the liquid crystal cell side (on the opposite side to the visibility side) of the polarizing film.
In such an image display device, since the polarized light passing through the polarizing film passes through the transparent conductive film, a substrate having a low phase difference (for example, a zero-phase-difference film) is required for the transparent substrate from the viewpoint of suppressing the elimination of the polarized light. Examples of the base film having such a low retardation include cycloolefin resins.
However, the cycloolefin resin is inferior in mechanical strength to PET or the like, and therefore, a disadvantage that the resin is easily broken at bending occurs. Therefore, improvement of substrate cracking is required.
On the other hand, when the formulation of the hard coat layer or the optical adjustment layer is changed to improve the substrate cracking, the scratch resistance, the pattern recognition suppression, and the like of the transparent conductive layer may not reach a desired level. Further, the transparent conductive film is required to have desired physical properties such as resistance to moist heat, patterning property, alkali resistance, and the like.
The invention provides a hard coating film, a transparent conductive film laminate and an image display device, which can realize suppression of substrate cracking and satisfy various physical properties required for optical applications.
The present invention [1] includes a hard coat film comprising a transparent base material and a hard coat layer disposed on one side of the transparent base material in a thickness direction, wherein the hard coat layer contains silica particles, zirconia particles, and a resin, a content ratio of the silica particles in the hard coat layer is 0.5% by mass or more and less than 3.0% by mass, and a content ratio of the zirconia particles in the hard coat layer is 35.0% by mass or more and less than 70.0% by mass.
The invention [2] comprises the hard coat film according to [1], wherein the transparent substrate is a cycloolefin-based substrate.
The invention [3] is the hard coat film according to [1] or [2], wherein the total content ratio of the silica particles and the zirconia particles in the hard coat layer is 65.0 mass% or less.
The invention [4] includes the hard coat film according to any one of [1] to [3], wherein the hard coat film has an elastic modulus of 4.2GPa or more.
The invention [5] includes the hard coat film according to any one of [1] to [4], wherein the hard coat film has a thickness of 0.7 μm or more and 2.0 μm or less.
The invention [6] includes a transparent conductive film comprising the hard coat film according to any one of [1] to [4] and a transparent conductive layer disposed on one side in the thickness direction of the hard coat film.
The invention [7] includes a transparent conductive film laminate comprising a polarizer and the transparent conductive film of [6 ].
The invention [8] includes an image display device comprising an image display element and the transparent conductive film laminate according to claim 7, wherein the transparent conductive film is disposed between the polarizer and the image display element.
The hard coat film, transparent conductive film laminate and image display device of the present invention are provided with a transparent substrate and a hard coat layer, and the hard coat layer contains silica particles, zirconia particles and a resin. The content ratio of the silica particles in the hard coat layer is 0.5 mass% or more and less than 3.0 mass%, and the content ratio of the zirconia particles in the hard coat layer is 35.0 mass% or more and less than 70.0 mass%. That is, in the hard coat film, the transparent conductive film laminate and the image display device of the present invention, the silica particles and the zirconia particles are present in the hard coat layer at a specific content ratio. Therefore, it is possible to realize a substrate that suppresses cracking and satisfies various physical properties required for optical applications (pattern recognition suppression, scratch resistance, wet heat resistance, patterning property, alkali resistance, when a transparent conductive layer is laminated).
Drawings
FIG. 1 shows a cross-sectional view of one embodiment of a hard coat film of the present invention.
Fig. 2A to 2B are sectional views of the transparent conductive film provided with the hard coating film shown in fig. 1, fig. 2A shows a sectional view of an unpatterned transparent conductive film, and fig. 2B shows a sectional view of a patterned transparent conductive film.
Fig. 3 is a sectional view of a transparent conductive thin film laminate including the transparent conductive thin film shown in fig. 2B.
Fig. 4 is a cross-sectional view of an image display device including the transparent conductive thin film laminate shown in fig. 3.
Detailed Description
One embodiment of each of the hard coat film, the transparent conductive film laminate, and the image display device according to the present invention will be described with reference to fig. 1 to 4.
In fig. 1, the vertical direction on the paper surface is the vertical direction (thickness direction, 1 st direction), the upper side on the paper surface is the upper side (thickness direction side, 1 st direction side), and the lower side on the paper surface is the lower side (thickness direction side, 1 st direction side). The horizontal direction and the depth direction of the drawing are plane directions orthogonal to the vertical direction. In particular according to the directional arrows of the figures.
1. Hard coating film
As shown in fig. 1, the hard coat film 1 has a film shape (including a sheet shape) having a predetermined thickness, extends in a predetermined direction (plane direction) perpendicular to the thickness direction, and has a flat upper surface and a flat lower surface.
The hard coat film 1 is a hard coat layer-attached film including a transparent base 2 and a hard coat layer 3 disposed on an upper surface (one surface in a thickness direction) of the transparent base 2. Preferably, the hard coat film 1 is composed of a transparent substrate 2 and a hard coat layer 3.
(transparent substrate)
The transparent substrate 2 is a transparent substrate for ensuring the mechanical strength of the hard coat film 1 (and further the transparent conductive film 4). That is, the transparent substrate 2 supports the hard coat layer 3, and the hard coat layer 3 and the transparent conductive layer 5 described later are supported on the transparent conductive film 4 described later.
The transparent substrate 2 is the lowermost layer of the hard coat film 1 and has a film shape. The transparent substrate 2 is disposed on the entire lower surface of the hard coat layer 3 so as to be in contact with the lower surface of the hard coat layer 3.
The transparent substrate 2 is, for example, a transparent polymer film. Examples of the material of the transparent substrate 2 include: polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; (meth) acrylic resins (acrylic resins and/or methacrylic resins) such as polymethacrylate; olefin resins such as polyethylene, polypropylene, and cycloolefin polymers (e.g., norbornene-based and cyclopentadiene-based resins); for example, polycarbonate resin, polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, and the like. The transparent substrate 2 may be used alone or in combination of 2 or more.
The transparent substrate 2 preferably includes a cycloolefin-based substrate (COP substrate) made of a cycloolefin polymer. When a COP substrate is used as the transparent substrate 2, the transparency is excellent. Further, since the COP substrate has a low in-plane birefringence and a substantially zero phase difference, the transparent conductive film laminate 8 described later can suppress the elimination of polarized light passing through the polarizer 10 and can reliably pass polarized light.
The total light transmittance (JIS K7375-2008) of the transparent substrate 2 is, for example, 80% or more, preferably 85% or more.
The in-plane birefringence of the transparent substrate 2 is, for example, 10nm or less, preferably 5nm or less. The in-plane birefringence can be measured, for example, by a birefringence measurement system (product name "AxoScan" manufactured by Axometrics inc.).
The thickness of the transparent base 2 is, for example, 2 μm or more, preferably 20 μm or more, and is, for example, 300 μm or less, preferably 150 μm or less, from the viewpoints of mechanical strength, dotting characteristics when the transparent conductive film 4 is used as a film for a touch panel, and the like. The thickness of the transparent substrate 2 can be measured, for example, using a micrometer thickness gauge.
(hard coating)
The hard coat layer 3 is a layer for suppressing breakage of the transparent substrate 2. In addition, the transparent conductive layer 5 is also a layer for suppressing the occurrence of damage in the transparent conductive layer 5 when the transparent conductive layer 5 is disposed.
The hard coat layer 3 is the uppermost layer of the hard coat film 1 and has a film shape. The hard coat layer 3 is disposed on the entire upper surface of the transparent substrate 2 so as to be in contact with the upper surface of the transparent substrate 2.
The hard coat layer 3 is a cured resin layer and is formed of a hard coat composition. The hard coating composition contains a resin and inorganic particles.
Examples of the resin include a curable resin and a thermoplastic resin (for example, a polyolefin resin), and a curable resin is preferably used.
Examples of the curable resin include: for example, an active energy ray-curable resin which is cured by irradiation with an active energy ray (specifically, ultraviolet ray, electron beam, or the like), a thermosetting resin which is cured by heating, or the like is preferable.
Examples of the active energy ray-curable resin include polymers having a functional group having a polymerizable carbon-carbon double bond in the molecule. Examples of such a functional group include a vinyl group, a (meth) acryloyl group (a methacryloyl group and/or an acryloyl group), and the like.
Specific examples of the active energy ray-curable resin include (meth) acrylic ultraviolet-curable resins such as urethane acrylate and epoxy acrylate.
Examples of the curable resin other than the active energy ray-curable resin include urethane resin, melamine resin, alkyd resin, silicone polymer, and organic silane condensate.
These resins may be used alone or in combination of 2 or more.
The content ratio of the resin is, for example, 30.0% by mass or more, preferably 35.0% by mass or more, and is, for example, 60.0% by mass or less, preferably 50.0% by mass or less, and more preferably 38.0% by mass or less with respect to the hard coating composition (i.e., hard coating layer 3). When the ratio is not less than the lower limit, the hard coat film 1 has excellent flexibility. When the ratio is not more than the upper limit, deterioration of the resin (hard coat layer 2) under high temperature and high humidity can be reduced, and therefore the transparent conductive film 4 is excellent in moist heat resistance.
The inorganic particles include silicon dioxide (SiO) 2 ) Particles and zirconia (ZrO) 2 ) And (3) granules. By providing the hard coat layer 3 with both silica particles and zirconia particles, cracking of the transparent base material 2 can be suppressed. In addition, for the hard coatingThe transparent conductive film 4 having the transparent conductive layer 5 laminated on the surface 3 can suppress the visibility of the pattern portion 6 (described later) and improve the abrasion resistance, the moist heat resistance, the patterning property, and the like. Further, since the hard coat layer 3 can be provided with an optical adjustment function, it is not necessary to provide a separate optical adjustment layer, and thus it is possible to realize a reduction in thickness and an improvement in productivity.
The silica particles have an average particle diameter of, for example, 1nm or more, preferably 5nm or more, and, for example, 50nm or less, preferably 20nm or less, and more preferably 15nm or less.
The average particle diameter of the inorganic particles (silica particles, zirconia particles, etc.) means the average particle diameter (D) of the particle size distribution on a volume basis 50 ) For example, a solution in which particles are dispersed in water can be measured by a light diffraction/scattering method.
The content ratio of the silica particles is 0.5% by mass or more and less than 3.0% by mass relative to the hard coating composition. Preferably 1.0 mass% or more and 2.8 mass% or less. When the content ratio of the silica particles is not less than the lower limit, the transparent conductive layer 5 can be more reliably adhered to the hard coat layer 3. Therefore, the transparent conductive layer 5 of the transparent conductive film 4 is excellent in scratch resistance, moist heat resistance, and patterning property. On the other hand, when the content ratio of the silica particles is not more than the upper limit, excessive breakage (dissolution, etc.) of the silica particles can be suppressed when the silica particles come into contact with chemicals such as alkali solutions and acid solutions, and the generation of cracks in the hard coat layer 3 can be suppressed. Therefore, the hard coat layer 3 is excellent in chemical resistance such as alkali resistance. In addition, the hard coat layer 3 on the lower side of the pattern portion 6 can be reliably held during patterning, and patterning properties are excellent.
The average particle diameter of the zirconia particles is, for example, 5nm or more, preferably 10nm or more, and is, for example, 100nm or less, preferably 50nm or less, and more preferably 40nm or less.
The content ratio of the zirconia particles is 35.0 mass% or more and less than 70.0 mass% with respect to the hard coating composition. Preferably 39.5% by mass or more, more preferably 45.0% by mass or more, further preferably 55.0% by mass or more, and further preferably 68.0% by mass or less, more preferably 65.0% by mass or less, further preferably 63.0% by mass or less. When the content ratio of the zirconia particles is not less than the lower limit, the refractive index of the hard coat layer 3 can be increased, and the hue difference (Δ E) can be reduced in the transparent conductive thin film 4 to suppress the visibility of the pattern portion 6. When the content ratio of the zirconia particles is not more than the upper limit, the hard coat film 1 has appropriate strength and toughness in the transparent base material 2 on which the hard coat layer 3 containing the silica particles is laminated, and therefore cracking thereof can be suppressed. Further, the phenomenon (bleeding) that zirconia particles aggregate and precipitate on the surface of the hard coat layer 3 can be suppressed, and the transmittance of the hard coat film 1 can be made good.
The mass ratio of the zirconia particles to the silica particles (mass of zirconia/mass of silica) is, for example, 10.0 times or more, preferably 18.0 times or more, and more preferably 22.0 times or more, and is, for example, 40.0 times or less, preferably 30.0 times or less, and more preferably 25.0 times or less. When the above ratio is within the above range, the transparent base material 2 is excellent in crack suppression, pattern recognition suppression (non-recognition), scratch resistance, moist heat resistance, and the like.
Examples of the inorganic particles include metal oxide particles containing titanium oxide, zinc oxide, tin oxide, or the like, and carbonate particles such as calcium carbonate, in addition to the above particles. As the inorganic particles, it is preferable to contain only silica particles and zirconia particles.
The total content ratio of the silica particles and the zirconia particles is, for example, 70.0 mass% or less, preferably 65.0 mass% or less, and is, for example, 40.0 mass% or more, preferably 50.0 mass% or more, and more preferably 62.0 mass% or more, with respect to the hard coating composition. When the total content ratio is not more than the upper limit, cracking of the transparent base material 2 in which the hard coat layer 3 containing silica particles is laminated can be suppressed. Further, bleeding of silica particles or zirconia particles can be more reliably suppressed on the surface of the hard coat layer 3, and the transmittance of the hard coat film 1 can be made good.
The content ratio of the inorganic particles is, for example, 70.0% by mass or less, preferably 65.0% by mass or less, and is, for example, 40.0% by mass or more, preferably 50.0% by mass or more, and more preferably 62.0% by mass or more, with respect to the hard coating composition. When the total content ratio is not more than the upper limit, cracking of the transparent substrate 2 and bleeding of the inorganic particles can be more reliably suppressed.
The content of the inorganic particles (particularly the total of the silica particles and the zirconia particles) is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, and is, for example, 300 parts by mass or less, preferably 200 parts by mass or less, with respect to 100 parts by mass of the resin.
The hard coat composition may further contain known additives such as a leveling agent, a thixotropic agent, and an antistatic agent.
The refractive index of the hard coat layer 3 is, for example, 1.55 or more, preferably 1.58 or more, more preferably 1.60 or more, and is, for example, 1.80 or less, preferably 1.75 or less, more preferably 1.70 or less. When the refractive index of the hard coat layer 3 is within the above range, the pattern portion 6 of the transparent conductive layer 5 can be inhibited from being recognized. The refractive index can be measured, for example, by an abbe refractometer.
The hard coat layer 3 has an elastic modulus of, for example, 4.0Gpa or more, preferably 4.2Gpa or more, more preferably 4.4Gpa or more, and further, for example, 10Gpa or less, preferably 5.8Gpa or less, more preferably 4.7Gpa or less. When the elastic modulus is not less than the lower limit, it is possible to improve the adhesion between the hard coat layer 3 and the transparent conductive layer 5 and to impart an appropriate elastic force to the transparent conductive layer 5 in which the hard coat layer 3 containing silica particles is laminated. Therefore, even if an impact (scratch) is applied to the transparent conductive layer 5 from the outside, the transparent conductive layer 5 is less likely to be damaged, and the transparent conductive layer 5 is less likely to be peeled off from the surface of the hard coat layer 3. As a result, excessive increase in the resistance value of the transparent conductive layer 5 due to scratching can be further suppressed, and the scratch resistance is further improved.
The amount of plastic deformation of the hard coat layer 3 is, for example, 50nm or more, preferably 60nm or more, and is, for example, 100nm or less, preferably 80nm or less. When the plastic deformation amount is within the above range, cracking of the transparent substrate 2 can be more reliably suppressed.
The elastic modulus and the amount of plastic deformation can be obtained by, for example, measuring the surface (upper surface) of the hard coat layer 3 with a nanoindenter under a condition of an indentation depth of 200 nm.
From the viewpoint of scratch resistance, the thickness of the hard coat layer 3 is, for example, 0.5 μm or more, preferably 0.7 μm or more, and is, for example, 10 μm or less, preferably 2.0 μm or less. The thickness of the hard coat layer 3 can be calculated based on the wavelength of the interference spectrum observed by the instantaneous multi-channel photometry system, for example.
(method for producing hard coating film)
Next, a method for producing the hard coat film 1 will be described.
First, a known or commercially available transparent substrate 2 is prepared.
If necessary, from the viewpoint of adhesion between the transparent base material 2 and the hard coat layer 3, the upper surface of the transparent base material 2 may be subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, or oxidation, or undercoating treatment. The transparent base material 2 may be subjected to dust removal and cleaning by solvent cleaning, ultrasonic cleaning, or the like.
Next, the hard coat layer 3 is provided on the upper surface of the transparent base material 2. For example, the hard coat layer 3 is formed on the upper surface of the transparent substrate 2 by wet coating the hard coat composition on the upper surface of the transparent substrate 2.
Specifically, for example, a solution (varnish) obtained by diluting the hard coat composition with a solvent is prepared, and the prepared hard coat composition solution is applied to the upper surface of the transparent substrate 2 and dried.
Examples of the solvent include an organic solvent and an aqueous solvent (specifically, water), and preferred examples thereof include an organic solvent. Examples of the organic solvent include alcohol compounds such as methanol, ethanol, and isopropanol, ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester compounds such as ethyl acetate and butyl acetate, ether compounds such as propylene glycol monomethyl ether, and aromatic compounds such as toluene and xylene. These solvents may be used alone or in combination of 2 or more.
The solid content concentration in the hard coat composition solution is, for example, 1 mass% or more, preferably 10 mass% or more, and is, for example, 30 mass% or less, preferably 20 mass% or less.
In the preparation of the hard coating composition solution, a silica particle dispersion liquid (silica sol) in which silica particles are dispersed in a solvent and a zirconia particle dispersion liquid in which zirconia particles are dispersed in a solvent are prepared, mixed with a resin, and then further diluted with a solvent.
The coating method can be appropriately selected depending on the hard coat composition solution and the transparent substrate 2. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire bar coating method, a gravure coating method, and an extrusion coating method.
The drying temperature is, for example, 50 ℃ or higher, preferably 70 ℃ or higher, for example 200 ℃ or lower, preferably 100 ℃ or lower.
The drying time is, for example, 0.5 minutes or more, preferably 1 minute or more, for example, 60 minutes or less, preferably 20 minutes or less.
When the hard coat composition contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating active energy rays after drying the hard coat composition solution.
When the hard coating composition contains a thermosetting resin, the drying step allows the thermosetting resin to be thermally cured while the solvent is dried.
Thereby, the hard coat film 1 was obtained.
If necessary, a functional layer such as an anti-blocking layer may be provided on the lower surface of the transparent base 2 of the hard coat film 1.
The thickness of the obtained hard coat film 1 is, for example, 2 μm or more, preferably 20 μm or more, and is, for example, 300 μm or less, preferably 150 μm or less.
(use)
The hard coat film 1 can be used for the transparent conductive film 4, for example. Specifically, the hard coat film 1 can be used as a support film for supporting the transparent conductive layer 5 in the transparent conductive film 4. The hard coat film 1 is, for example, one member for producing a transparent conductive film 4, a transparent conductive film laminate 8, an image display device 11, and the like, which will be described later. That is, the hard coat film 1 is a device that is distributed as a single member and is industrially applicable, without including the transparent conductive layer 5, the polarizer 10, and the image display element 14 (liquid crystal cell, etc.), which will be described later.
Further, the hard coat film 1 can suppress cracking of the transparent substrate 2 (particularly, a cycloolefin-based substrate which is a flexible substrate) when it is bent. At the same time, the composition satisfies various physical properties required for optical applications (particularly for touch panel applications) in a well-balanced manner. Specifically, when the transparent conductive layer 5 is formed on the hard coat layer 3 of the hard coat film 1, the non-visibility of the pattern portion 6 (described later), the abrasion resistance of the transparent conductive layer 5, the moisture and heat resistance of the transparent conductive layer 5, the patterning property of the transparent conductive layer 5, the alkali resistance of the hard coat layer 3, and the like are good.
2. Transparent conductive film
As shown in fig. 2A, the transparent conductive film 4 has a film shape having a predetermined thickness, extends in the plane direction, and has a flat upper surface and a flat lower surface.
The transparent conductive film 4 includes a hard coat film 1 and a transparent conductive layer 5 disposed on the upper surface thereof. That is, the transparent conductive thin film 4 includes the transparent base 2, the hard coat layer 3 disposed on the upper surface of the transparent base 2, and the transparent conductive layer 5 disposed on the upper surface of the hard coat layer 3. The transparent conductive thin film 4 is preferably composed of a transparent substrate 2, a hard coat layer 3, and a transparent conductive layer 5.
(transparent conductive layer)
The transparent conductive layer 5 is a conductive layer for forming a transparent pattern portion 6 (see fig. 2B) and a non-pattern portion 7 by crystallizing as necessary and forming a desired pattern in a subsequent step.
The transparent conductive layer 5 is the uppermost layer of the transparent conductive film 4 and has a film shape. The transparent conductive layer 5 is disposed on the entire upper surface of the hard coat layer 3 so as to contact the upper surface of the hard coat layer 3.
Examples of the material of the transparent conductive layer 5 include metal oxides containing at least 1 metal selected from the group consisting of In, sn, zn, ga, sb, ti, si, zr, mg, al, au, ag, cu, pd, and W. The metal oxide may be further doped with metal atoms shown in the above group as necessary.
Specific examples of the transparent conductive layer 5 include: for example, an indium-containing oxide such as indium tin composite oxide (ITO), an antimony-containing oxide such as antimony tin composite oxide (ATO), and the like, and preferably an indium-containing oxide, and more preferably ITO.
When the transparent conductive layer 5 is an indium tin composite oxide layer such as an ITO layer, the transparent conductive layer is formed by combining tin oxide and indium oxide (In) 2 O 3 ) Total amount of (B), tin oxide (SnO) 2 ) The content ratio is, for example, 0.5% by mass or more, preferably 5% by mass or more, and is, for example, 30% by mass or less, preferably 25% by mass or less. When the content ratio of tin oxide is not less than the lower limit, the durability of the transparent conductive layer 5 can be further improved. When the content ratio of tin oxide is not more than the upper limit, crystal transformation of the transparent conductive layer 5 can be easily performed, and stability of transparency and surface resistance can be improved.
The "ITO" In the present specification may contain an additional component other than the above as long as it is a composite oxide containing at least indium (In) and tin (Sn). Examples of the additional component include metal elements other than In and Sn, and specifically include Zn, ga, sb, ti, si, zr, mg, al, au, ag, cu, pd, W, fe, pb, ni, nb, cr, ga, and the like.
The surface resistance of the transparent conductive layer 5 is, for example, 20 Ω/\9633, 70 Ω/\9633, or more and less. The surface resistance can be measured by the 4-terminal method.
The thickness of the transparent conductive layer 5 is, for example, 10nm or more, preferably 30nm or more, and is, for example, 50nm or less, preferably 40nm or less. The thickness of the transparent conductive layer 5 can be measured, for example, using an instantaneous multi-channel photometric system.
The transparent conductive layer 5 may be either amorphous or crystalline.
Whether the transparent conductive layer 5 is amorphous or crystalline can be determined, for example, as follows: when the transparent conductive layer is an ITO layer, it is determined by immersing the transparent conductive layer in hydrochloric acid (concentration 5 mass%) at 20 ℃ for 15 minutes, washing and drying the layer, and measuring the resistance between terminals of about 15 mm. In the present specification, after immersion in hydrochloric acid (20 ℃ C., concentration: 5% by mass), washing with water and drying, the ITO layer was considered amorphous when the inter-terminal resistance between 15mm exceeded 10 kOmega, and crystalline when the inter-terminal resistance between 15mm was 10 kOmega or less.
(method for producing transparent conductive film)
Next, a method for producing the transparent conductive thin film 4 will be described.
In order to produce the transparent conductive film 4, the hard coat film 1 is prepared, and the transparent conductive layer 5 is formed on the upper surface of the hard coat layer 3 by, for example, a dry method.
Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method. Sputtering is preferably used. By this method, the transparent conductive layer 5 can be formed as a thin film.
In the case of sputtering, the target material may be the inorganic material constituting the transparent conductive layer 5, and ITO is preferably used. The tin oxide concentration of the ITO is, for example, 0.5 mass% or more, preferably 3 mass% or more, and, for example, 15 mass% or less, preferably 13 mass% or less, from the viewpoint of durability, crystallization, and the like of the ITO layer.
Examples of the sputtering gas include inert gases such as Ar. Further, reactive gases such as oxygen may be used in combination as necessary. When the reactive gases are used in combination, the flow ratio of the reactive gases is not particularly limited, and is, for example, 0.1 to 5% by flow relative to the total flow ratio of the sputtering gas and the reactive gas.
The sputtering process is carried out under vacuum. Specifically, from the viewpoints of suppressing a decrease in the sputtering rate, discharge stability, and the like, the gas pressure during sputtering is, for example, 1Pa or less, preferably 0.7Pa or less.
The power source used for the sputtering method may be any of a DC power source, an AC power source, an MF power source, and an RF power source, or a combination thereof.
In order to form the transparent conductive layer 5 having a desired thickness, sputtering may be performed a plurality of times by appropriately setting a target, sputtering conditions, and the like.
As a result, the transparent conductive film 4 including the transparent base 2, the hard coat layer 3, and the transparent conductive layer 5 in this order can be obtained as shown in fig. 2A. The transparent conductive film 4 is a non-patterned transparent conductive film that is not subjected to patterning treatment.
The thickness of the transparent conductive thin film 4 is, for example, 2 μm or more, preferably 20 μm or more, and is, for example, 100 μm or less, preferably 50 μm or less.
Next, as shown in fig. 2B, the transparent conductive layer 5 is patterned by performing known etching on the transparent conductive thin film as necessary.
The pattern of the transparent conductive layer 5 may be determined as appropriate depending on the application of the transparent conductive film 4, and examples thereof include an electrode pattern such as a stripe pattern and a wiring pattern.
For example, the etching is performed by disposing a coating portion (mask tape or the like) on the transparent conductive layer 5 so as to correspond to the pattern portion 6 and the non-pattern portion 7, and etching the transparent conductive layer 5 (non-pattern portion 7) exposed from the coating portion with an etching solution. Examples of the etching solution include acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, phosphoric acid, and mixed acids thereof. Then, the covered portion is removed from the upper surface of the transparent conductive layer 5 by, for example, peeling.
As a result, as shown in fig. 2B, the transparent conductive film 4 in which the transparent conductive layer 5 is patterned can be obtained. That is, the patterned transparent conductive film 4 including the pattern portion 6 and the non-pattern portion 7 can be obtained.
If necessary, the transparent conductive layer 5 of the transparent conductive thin film 4 is subjected to a crystallization conversion treatment before or after etching.
Specifically, the transparent conductive film 4 is subjected to heat treatment in the air.
The heat treatment can be performed using, for example, an infrared heater, an oven, or the like.
The heating temperature is, for example, 100 ℃ or higher, preferably 120 ℃ or higher, and is, for example, 200 ℃ or lower, preferably 160 ℃ or lower. When the heating temperature is within the above range, thermal damage to the transparent substrate 2 and impurities generated from the transparent substrate 2 can be suppressed, and crystal transformation can be reliably performed.
The heating time is appropriately determined depending on the heating temperature, and is, for example, 10 minutes or more, preferably 30 minutes or more, and is, for example, 5 hours or less, preferably 3 hours or less.
This makes it possible to obtain the transparent conductive film 4 in which the transparent conductive layer 5 is crystallized.
The difference Δ E (hue difference) in transmittance between the pattern portion 6 and the non-pattern portion 7 in the transparent conductive film 4 is, for example, 4.0 or less, preferably 3.0 or less. When the transmittance difference Δ E is within the above range, the pattern portion 6 such as the electrode pattern can be prevented from being recognized.
Regarding the transmittance difference Δ E, L in the pattern portion 6 can be measured 1 、a* 1 、b* 1 And L in the non-pattern portion 7 2 、a* 2 、b* 2 And calculated according to the following formula.
ΔE＝{(L 2 -L 1 ) 2 +(a* 2 -a* 1 ) 2 +(b* 2 -b* 1 ) 2 } 1/2
The difference Δ E in transmittance can be obtained by measuring the difference in transmittance in the wavelength region of 380nm to 800nm using, for example, an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi High-Tech Science Corporation, "U4100").
(use)
The transparent conductive film 4 is used as a substrate for a touch panel provided in an optical device such as an image display device 11 (described later). Examples of the form of the touch panel include various forms such as an optical type, an ultrasonic type, a capacitive type, and a resistive type, and the touch panel is particularly preferably used for a capacitive type touch panel.
The transparent conductive film 4 is a member used for manufacturing the transparent conductive film laminate 8, the image display device 11, and the like. That is, the transparent conductive film 4 is a device that is distributed as a single member and is industrially applicable, without including the polarizer 10 and the image display element 14.
Further, the transparent conductive film 4 can suppress cracking of the transparent substrate 2 (particularly, a cycloolefin-based substrate which is a flexible substrate) when it is bent. At the same time, the composition satisfies various physical properties required for optical use in a well-balanced manner. Specifically, the transparent conductive film 4 is excellent in the non-visibility, the scratch resistance, the moist heat resistance, the patterning property, the alkali resistance, and the like of the pattern portion 6.
3. Transparent conductive film laminate
As shown in fig. 3, the transparent conductive thin film laminate 8 has a thin film shape having a predetermined thickness, extends in the planar direction, and has a flat upper surface and a flat lower surface.
The transparent conductive film laminate 8 includes a transparent conductive film 4, and a 1 st pressure-sensitive adhesive layer 9 and a polarizer 10 disposed on the upper surface thereof. That is, the transparent conductive thin film laminate 8 includes: a transparent substrate 2, a hard coat layer 3 disposed on the upper surface of the transparent substrate 2, a transparent conductive layer 5 disposed on the upper surface of the hard coat layer 3, a 1 st adhesive layer 9 disposed on the upper surface of the transparent conductive layer 5, and a polarizer 10 disposed on the upper surface of the 1 st adhesive layer 9. The transparent conductive thin film laminate 8 preferably comprises a transparent substrate 2, a hard coat layer 3, a transparent conductive layer 5, a 1 st adhesive layer 9, and a polarizer 10. In the transparent conductive thin film laminate 8, the transparent conductive layer 5 is preferably patterned and includes a pattern portion 6 and a non-pattern portion 7.
(No. 1 adhesive layer)
The 1 st adhesive layer 9 is a layer for bonding the transparent conductive film 4 and the polarizer 10.
The 1 st adhesive layer 9 has a film shape. The 1 st adhesive layer 9 is disposed on the entire upper surface of the transparent conductive layer 5 (pattern portion 6) and the hard coat layer 3 (non-pattern portion 7) exposed therefrom so as to contact the upper surface of the transparent conductive layer 5. The 1 st adhesive layer 9 is disposed on the entire lower surface of the polarizer 10 so as to contact the lower surface of the polarizer 10.
Examples of the material of the 1 st pressure-sensitive adhesive layer 9 include acrylic pressure-sensitive adhesives, butyl rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, polyester pressure-sensitive adhesives, polyurethane pressure-sensitive adhesives, polyamide pressure-sensitive adhesives, epoxy pressure-sensitive adhesives, vinyl alkyl ether pressure-sensitive adhesives, and fluororesin pressure-sensitive adhesives.
The thickness of the 1 st pressure-sensitive adhesive layer 9 is, for example, 1 μm or more, preferably 10 μm or more, and is, for example, 300 μm or less, preferably 150 μm or less.
(polarizing element)
The polarizer 10 is a layer for converting light into linearly polarized light.
The polarizer 10 is the uppermost layer of the transparent conductive thin film laminate 8 and has a thin film shape. The polarizer 10 is disposed on the entire upper surface of the 1 st adhesive layer 9 so as to contact the upper surface of the 1 st adhesive layer 9.
Examples of the polarizer 10 include a polyvinyl alcohol film containing iodine.
Examples of the material of the polyvinyl alcohol film include polyvinyl alcohol and derivatives thereof. Examples of the derivative include polyvinyl formal and polyvinyl acetal. Examples of the derivative include modified polyvinyl alcohols obtained by modifying polyvinyl alcohols with olefins (e.g., ethylene and propylene), unsaturated carboxylic acids (e.g., acrylic acid and methacrylic acid), acrylamide, and the like.
The polarizer 10 can be obtained by adding iodine to a film made of vinyl alcohol or a derivative thereof and then stretching the film.
Such polarizers are described in, for example, japanese patent laid-open Nos. Sho 51-069644, 2000-338329, WO 2010/100917, japanese patent No. 4691205, and Japanese patent No. 4751481.
The polarizer 10 may be provided with a protective film on each of the upper and lower surfaces of the polyvinyl alcohol film. That is, the polarizer 10 may be a laminate including a polyvinyl alcohol film and protective films disposed on both surfaces thereof. Examples of the material of the protective film include the material of the transparent substrate 2.
The thickness of the polarizer 10 is, for example, 1 μm or more, preferably 5 μm or more, and is, for example, 200 μm or less, preferably 100 μm or less.
The transparent conductive film laminate 8 can be produced, for example, as follows: the transparent conductive film is manufactured by applying a liquid adhesive or disposing an adhesive tape on the upper surface of the transparent conductive film 4 to form a 1 st adhesive layer 9, and then disposing a polarizer 10 on the upper surface of the 1 st adhesive layer 9.
(use)
The transparent conductive film laminate 8 can be used as a substrate for a touch panel provided in an optical device such as the image display device 11, for example.
The transparent conductive thin film laminate 8 is a member used for manufacturing the image display device 11 and the like. That is, the transparent conductive film 4 is a device that is distributed as a separate member and industrially applicable, without including the image display element 14.
Further, the transparent conductive film laminate 8 can suppress cracking of the transparent substrate 2 (particularly, a cycloolefin-based substrate which is a flexible substrate) when it is bent. At the same time, the composition satisfies the properties required for optical applications in a well-balanced manner. Specifically, the transparent conductive thin film laminate 8 is excellent in the non-visibility, scratch resistance, moist heat resistance, patterning property, alkali resistance, and the like of the pattern portion 6.
4. Image display device
As shown in fig. 4, the image display device 11 includes: a transparent conductive thin film laminate 8, a 2 nd pressure-sensitive adhesive layer 12 and a transparent protective plate 13 disposed on the upper surface thereof, and an image display element 14 disposed to face the lower surface thereof. That is, the image display device 11 includes, in order in the thickness direction: an image display element 14, a transparent substrate 2, a hard coat layer 3, a transparent conductive layer 5, a 1 st adhesive layer 9, a polarizer 10, a 2 nd adhesive layer 12, and a transparent protective plate 13. In fig. 4, the upper side is the recognition side, and the lower side is the image display element side.
(No. 2 adhesive layer)
The 2 nd pressure-sensitive adhesive layer 12 is a layer for bonding the transparent conductive thin film laminate 8 and the transparent protective plate 13.
The 2 nd adhesive layer 12 has a film shape. The 2 nd adhesive layer 12 is disposed on the entire upper surface of the polarizer 10 and the entire lower surface of the transparent protective plate 13 so as to contact the upper surface of the polarizer 10 and the lower surface of the transparent protective plate 13.
Examples of the material of the 2 nd adhesive layer 12 include the same materials as those described for the 1 st adhesive layer 9.
The thickness of the 2 nd pressure-sensitive adhesive layer 12 is, for example, 1 μm or more, preferably 5 μm or more, and is, for example, 300 μm or less, preferably 150 μm or less.
(transparent protective plate)
The transparent protective plate 13 is a layer for protecting internal members of the image display device such as the image display element 14 from external impact and contamination.
The transparent protective plate 13 has a substantially flat plate shape in plan view, and is disposed on the entire upper surface of the 2 nd adhesive layer 12 so as to contact the upper surface of the 2 nd adhesive layer 12.
The transparent protective plate 13 has transparency, and has an appropriate thickness and mechanical strength.
Examples of the transparent protective plate 13 include a resin plate made of a hard resin such as an acrylic resin or a polycarbonate resin, for example, a glass plate, and the like.
The thickness of the transparent protective plate 13 is, for example, 10 μm or more, preferably 500 μm or more, and is, for example, 10mm or less, preferably 5mm or less.
(image display element)
The image display element 14 is disposed opposite to the hard coat film 1 with a gap.
As the image display element 14, for example, a liquid crystal cell can be cited. The liquid crystal cell is not shown, and includes a liquid crystal layer, a polarizer disposed below the liquid crystal layer, and a color filter.
Since the image display device 11 includes the transparent conductive film 4, the pattern portion 6 of the transparent conductive layer 5 is inhibited from being recognized, and excellent durability is exhibited.
Examples
The present invention will be further specifically described below by way of examples and comparative examples. The present invention is not limited to the examples and comparative examples. In addition, specific numerical values of the blending ratio (content ratio), physical property value, parameter, and the like used in the following description may be substituted for the upper limit value (defined as "lower" or "lower" numerical value) or the lower limit value (defined as "upper" or "upper" numerical value) corresponding to the blending ratio (content ratio), physical property value, parameter, and the like described in the above "specific embodiment".
(hard coating film)
Example 1
As the transparent substrate, a cycloolefin resin film (thickness: 40 μm, manufactured by Nippon Ralstonia, "ZEONOR ZF-16", in-plane birefringence: 5 nm) was prepared.
A hard coat composition solution having a solid content of 16 mass% was prepared by mixing an ultraviolet-curable urethane acrylate (UA-160 (TM) available from Nippon Komura chemical Co., ltd.), a silica dispersion (silica sol, average particle diameter 10nm, methyl ethyl ketone solvent, MEK-ST-40 available from Nissan chemical industries, ltd.), and a zirconia dispersion (average particle diameter 15 to 40nm, OZ-S30K available from Nissan chemical industries, ltd.) so that the mass ratios of the urethane acrylate, silica particles and zirconia were 58.0 mass%, 2.5 mass% and 39.5 mass%, and adding butyl acetate to the mixture.
The hard coat composition solution was applied onto the upper surface of a transparent substrate using a wire bar, dried at 80 ℃ for 1 minute, and then irradiated with ultraviolet light using an air-cooled mercury lamp to cure the hard coat composition. Thus, a hard coat layer having a thickness of 1.0 μm was formed on the upper surface of the transparent substrate to produce a hard coat film.
Examples 2 to 6
A hard coat film was produced in the same manner as in example 1, except that the ratio of the urethane acrylate, the silica particles and the zirconia in the hard coat composition was changed to the ratio described in table 1.
Comparative example 1
A hard coat film was produced in the same manner as in example 1, except that only urethane acrylate (product of DIC corporation, "ELS 888") was used as the hard coat composition.
Comparative example 2
A hard coat film was produced in the same manner as in example 1, except that the ratio of the urethane acrylate, the silica particles and the zirconia in the hard coat composition was changed to the ratio described in table 1.
Comparative example 3
A hard coat film was produced in the same manner as in example 1, except that "KZ6506" (containing 60 mass% of urethane acrylate and 40 mass% of silica particles) manufactured by JSR corporation was used as the hard coat composition.
Comparative example 4
A hard coat film was produced in the same manner as in example 1, except that "KZ6519" (containing 40 mass% of urethane acrylate and 60 mass% of silica particles) manufactured by JSR corporation was used as the hard coat composition.
Comparative example 5
A hard coat film was produced by forming a hard coat layer having a thickness of 1.0 μm on the upper surface of the transparent substrate in the same manner as in example 1 except that a diluted solution of an ultraviolet-curable acrylic resin (manufactured by Aica Kogyo Company, "Z-850-6L") was used as a hard coat composition solution.
Next, as a composition solution for an optical adjustment layer, a diluted solution of a mixture of "KZ7412" and "KZ7416" (containing 40 mass% of urethane acrylate and 60 mass% of zirconia grains) manufactured by JSR corporation was prepared. The composition solution for optical adjustment layer was applied on the upper surface of the hard coat layer and dried, and then irradiated with ultraviolet rays to form an optical adjustment layer having a thickness of 0.1 μm.
Thus, a hard coat film with an optical adjustment layer, which comprises a transparent base material, a hard coat layer, and an optical adjustment layer in this order, was produced.
(transparent conductive film)
In the hard coat films of the examples and comparative examples, an amorphous ITO layer (transparent conductive layer) having a thickness of 40nm was formed on the upper surface of the hard coat layer by DC sputtering. Specifically, an ITO target formed of a sintered body of 90 mass% indium oxide and 10 mass% tin oxide was sputtered in a vacuum atmosphere of 0.4Pa in pressure in which 98% argon gas and 2% oxygen gas were introduced. In comparative examples 5 to 6, an ITO layer was provided on the upper surface of the optical adjustment layer.
Thus, a transparent conductive film was produced.
(measurement of refractive index)
For the hard coat layers of the hard coat films of the examples and comparative examples, the refractive index of the hard coat layer was measured using an abbe refractometer. In comparative example 5, the refractive index of the optical adjustment layer was measured. The results are shown in Table 1.
(measurement of elastic modulus and amount of Plastic deformation)
For the hard coat layer of the hard coat film of each example and each comparative example, the elastic modulus at a depth of 200nm was measured using a nanoindenter under the following conditions. In comparative example 5, the elastic modulus of the optical adjustment layer was measured. The results are shown in Table 1.
Nano-indentation instrument: "Triboindeter" manufactured by Hysitoton corporation "
Pressure head: berkobich (triangular pyramid type)
Measurement mode: single press-in
Measuring temperature: room temperature (25 ℃ C.)
Pressing depth: 200nm
(substrate cracking)
The hard coat films of examples and comparative examples were subjected to a 180 ° bend test with the transparent substrate side facing inward. The surface of the transparent base material after the test was observed, and the case where no breakage of the transparent base material was visually observed was evaluated as good, the case where very small breakage of the edge of the transparent base material was observed was evaluated as Δ, and the case where breakage of the transparent base material was observed was evaluated as x. The results are shown in Table 1.
(measurement of patterning Property, non-visibility of pattern, and transmittance Difference Δ E)
The transparent conductive films of examples and comparative examples were heated at 130 ℃ for 90 minutes to crystallize the transparent conductive layer. Then, an adhesive tape (width 1 cm) was attached in stripes at 1cm intervals to the surface of the transparent conductive layer of the crystallized transparent conductive film, and the transparent conductive layer was etched with 10 mass% hydrochloric acid at 50 ℃. Thus, a pattern portion having a width of 1cm and a non-pattern portion having a width of 1cm were formed (see FIG. 2B).
Patterning: the surface of the pattern portion of the transparent conductive layer was observed with a microscope (magnification 20 times), and the case where no crack was observed was evaluated as good, and the case where crack was observed was evaluated as poor.
Non-distinguishability of the pattern: the transparent conductive film was irradiated from the transparent conductive layer side with a fluorescent lamp and observed visually from the transparent substrate side, the case where the distinction between the pattern portion and the non-pattern portion could not be confirmed was evaluated as good, the case where the pattern portion and the non-pattern portion could be slightly confirmed was evaluated as Δ, and the case where the pattern portion and the non-pattern portion could be clearly confirmed was evaluated as x.
Transmittance difference Δ E: l in the pattern portion was measured in a wavelength region of 380nm to 800nm using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi High-Tech Science Corporation, U4100) 1 、a* 1 、b* 1 And L in the non-pattern portion 2 、a* 2 、b* 2 . Then, they were calculated from the following formula.
ΔE＝{(L 2 -L 1 ) 2 +(a* 2 -a* 1 ) 2 +(b* 2 -b* 1 ) 2 } 1/2
These results are shown in Table 1.
(scratch resistance)
The transparent conductive films of examples and comparative examples were heated at 130 ℃ for 90 minutes to crystallize the transparent conductive layer. Next, an industrial wiper (manufactured by CONTEC, "anti, gold Sorb") was pressed against the surface of the transparent conductive layer of the crystallized transparent conductive film so as to have a load of 400g in a range of 11mm in diameter, and slid 5 times between 10cm in length. Then, a 4-probe type probe was placed on the surface of the transparent conductive layer so as to measure in the orthogonal direction orthogonal to the sliding direction, and the surface resistance value R of the transparent conductive thin film after sliding was measured 10 . In addition, will be transparent before slidingThe surface resistance value of the conductive thin film at the same position is taken as R 0 。
The rate of change (R) of the surface resistance value 10 /R 0 ) The evaluation was good when the value was less than 2, Δ when the value was 2 or more and less than 5, and x when the value was 5 or more. The results are shown in Table 1.
(moist-heat resistance)
The transparent conductive films of examples and comparative examples were heated at 130 ℃ for 90 minutes to crystallize the transparent conductive layer. Subsequently, the crystallized transparent conductive film was left to stand at 85% RH at 85 ℃ for 240 hours, and subjected to a 100-cell cross-cut test.
The evaluation was good when the number of lattices in which the transparent conductive layer was peeled off was less than 20, good when 20 or more and less than 50 were evaluated as Δ, and good when 50 or more were evaluated as x. The results are shown in Table 1.
(alkali resistance)
The transparent conductive films of examples and comparative examples were heated at 130 ℃ for 90 minutes to crystallize the transparent conductive layer. Subsequently, a slit having a length of 1cm was formed in the crystallized transparent conductive film by a cutter, and the film was immersed in a 3 mass% aqueous solution of KOH (temperature 30 ℃ C.) for 20 minutes. The cut portion was observed with a microscope (magnification 20 times), and the case where no crack was observed in the hard coat layer was evaluated as good, and the case where crack was observed was evaluated as poor.
The results are shown in Table 1.
[ Table 1]
Figure BDA0002022838930000241
The above-described invention provides an exemplary embodiment of the present invention, but this is merely an example and is not to be construed as limiting. Variations of the present invention that are obvious to those skilled in the art are also within the scope of protection.

Claims (8)

1. A hard coat film characterized by comprising:
transparent substrate, and
a hard coat layer disposed on one side in the thickness direction of the transparent base material,
the hard coat layer contains silica particles, zirconia particles, and a resin, the silica particles having an average particle diameter of 1nm or more and 50nm or less,
the content ratio of the silica particles in the hard coat layer is 0.5% by mass or more and less than 3.0% by mass,
the content ratio of the zirconia particles in the hard coat layer is 35.0 mass% or more and less than 70.0 mass%.
2. The hardcoat film of claim 1 wherein the transparent substrate is a cycloolefin-based substrate.
3. The hard coating film according to claim 1 or 2, wherein a total content ratio of the silica particles and the zirconia particles in the hard coating layer is 65.0% by mass or less.
4. The hard coat film according to claim 1 or 2, wherein the elastic modulus of the hard coat film is 4.2GPa or more.
5. The hard coat film according to claim 1 or 2, wherein the thickness of the hard coat film is 0.7 μm or more and 2.0 μm or less.
6. A transparent conductive film, comprising:
the hard coat film as defined in claim 1 or 2, and
and a transparent conductive layer disposed on one side of the hard coat film in the thickness direction.
7. A transparent conductive thin film laminate, comprising:
polarizing element and
the transparent conductive film of claim 6.
8. An image display device is characterized by comprising:
image display element, and
a transparent conductive thin film laminate according to claim 7,
the transparent conductive film is disposed between the polarizer and the image display element.
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